Metal catalyst and its use

ABSTRACT

A metal catalyst obtained by contacting
     (A) at least one metal or metal compound selected from   i) tungsten compounds composed of tungsten and an element of group IIIb, IVb, Vb, or VIb,   ii) molybdenum compounds composed of molybdenum and an element of group IIIb, IVb, Vb, or VIb, and   iii) tungsten metal and molybdenum metal;   (B) at least one compound selected from tertiary amine compounds, tertiary amine oxide compounds, nitrogen-containing aromatic compounds and nitrogen-containing aromatic N-oxide compounds;   (C) hydrogen peroxide; and   (D) a phosphate compound, is provided.

TECHNICAL FIELD

The present invention provides a novel metal catalyst and its use.

BACKGROUND ART

Epoxides are important compounds as various chemicals including resinand the synthetic intermediates for them, and for example, a method forproducing cyclooctene oxide by reacting cyclooctene with hydrogenperoxide using tungsten peroxo complex catalyst havingdimethyloctadecylamine oxide as a ligand is described (e.g. JP 11-512335A).

DISCLOSURE OF INVENTION

According to the present invention, it is possible to produce anepoxide, a β-hydroxyhydroperoxide compound or a carbonyl compound froman olefin easily.

That is, the present invention provides a metal catalyst obtained bycontacting

(A) at least one metal or metal compound selected from

i) tungsten compounds composed of tungsten and an element of group IIIb,IVb, Vb, or VIb,

ii) molybdenum compounds composed of molybdenum and an element of groupIIIb, IVb, Vb, or VIb and

iii) tungsten metal and molybdenum metal;

(B) at least one compound selected from tertiary amine compounds,tertiary amine oxide compounds, nitrogen-containing aromatic compoundsand nitrogen-containing aromatic N-oxide compounds;

(C) hydrogen peroxide; and

(D) a phosphate compound, and its use.

BEST MODE FOR CARRYING OUT THE INVENTION

First, the metal catalyst of the present invention will be illustrated.

Examples of the tungsten compound consisting of tungsten and theabove-mentioned element of group IIIb in (A) include tungsten boride.Examples of the tungsten compound consisting of tungsten and the elementof group IVb include tungsten carbide and tungsten silicide. Examples ofthe tungsten compound consisting of tungsten and the element of group Vbinclude tungsten nitride and tungsten phosphide. Examples of thetungsten compound consisting of tungsten and the element of group VIbinclude tungsten oxide, tungstic acid, sodium tungstate and tungstensulfide.

Examples of the molybdenum compound consisting of molybdenum and theelement of group IIIb include molybdenum boride. Examples of themolybdenum compound consisting of molybdenum and the element of groupIVb include molybdenum carbide and molybdenum silicide. Examples of themolybdenum compound consisting of molybdenum and the element of group Vbinclude molybdenum nitride and molybdenum phosphide. Examples of themolybdenum compound consisting of molybdenum and the element of groupVIb include molybdenum oxide, molybdic acid and molybdenum sulfide.

Among the metal or metal compound, tungsten metal, tungsten boride,sodium tungstate and molybdenum metal are especially preferable.Further, the metal or metal compound may be used alone, or two or moreof them may be used by mixing. Furthermore, it is preferred to use themetal or metal compound having a smaller particle size because the metalcatalyst can be easily prepared.

Among the compound in (B) group, examples of the tertiary amine includetrimethylamine, triethylamine, tri(n-propyl)amine, triisopropylamine,tri(n-butyl)amine, triisobutylamine, tri(n-pentyl)amine,tri(n-hexyl)amine, tri(n-heptyl)amine, tri(n-octyl)amine,tri(n-nonyl)amine, tri(n-decyl)amine, tri(n-dodecyl)amine,tri(n-tetradecyl)amine, tri(n-hexadecyl)amine, tri(n-octadecyl)amine,dimethylethylamine, dimethyl(n-propyl)amine, dimethylisopropylamine,dimethyl(n-butyl)amine, dimethylisobutylamine, dimethyl(n-pentyl)amine,dimethyl(n-hexyl)amine, dimethyl(n-heptyl)amine, dimethyl(n-octyl)amine,dimethyl(n-nonyl)amine, dimethyl(n-decyl)amine,dimethyl(n-undecyl)amine, dimethyl(n-dodecyl)amine,dimethyl(n-tetradecyl)amine, dimethyl(n-hexadecyl)amine,dimethyl(n-octadecyl)amine, methyldiethylamine, di(n-propyl)methylamine,diisopropylmethylamine, di(n-butyl)methylamine, diisobutylmethylamine,di(n-pentyl)methylamine, di(n-hexyl)methylamine,di(n-heptyl)methylamine, di(n-octyl)methylamine, di(n-nonyl)methylamine,di(n-decyl)methylamine, di(n-dodecyl)methylamine,di(n-tetradecyl)methylamine, di(n-hexadecyl)methylamine,di(n-octadecyl)methylamine, dimethylbenzylamine, di(n-butyl)benzylamine,di(n-hexyl)benzylamine, di(n-octyl)benzylamine, di(n-decyl)benzylamine,di(n-dodecyl)benzylamine, di(n-octadecyl)benzylamine,N,N-dimethylaniline, N,N-di(n-butyl)aniline, N,N-di(n-hexyl)aniline,N,N-di(n-octyl)aniline, N,N-di(n-decyl)aniline,N,N-di(n-dodecyl)aniline, N,N-di(n-octadecyl)aniline,N-methylmorpholine, N-(n-butyl)morpholine, N-(n-hexyl)morpholine,N-(n-octyl)morpholine, N-(n-decyl)morpholine, N-(n-dodecyl)morpholine,N-(n-hexadecyl)morpholine, N-(n-octadecyl)morpholine,N-methylpyrrolidine, N-(n-butyl)pyrrolidine, N-(n-hexyl)pyrrolidine,N-(n-octyl)pyrrolidine, N-(n-decyl)pyrrolidine,N-(n-dodecyl)pyrrolidine, N-(n-hexadecyl)pyrrolidine,N-(n-octadecyl)pyrrolidine, N-methylpiperidine, N-(n-butyl)piperidine,N-(n-hexyl)piperidine, N-(n-octyl)piperidine, N-(n-decyl)piperidine,N-(n-dodecyl)piperidine, N-(n-hexadecyl)piperidine andN-(n-octadecyl)piperidine.

Examples of the tertiary amine oxide include the compound in which anitrogen atom composed of the amino group of the above-mentionedtertiary amine was oxidized such as trimethylamine N-oxide,triethylamine N-oxide and N-methylmorpholine N-oxide. Asnitrogen-containing aromatic compound, the compound in which at leastone carbon atom selected from carbon atoms composed of the aromatic ringis replaced by a nitrogen atom such as pyridine, 2-methylpyridine,3-methylpyridine, 4-methylpyridine, 4-ethylpyridine,4-(n-butyl)pyridine, 4-(1-hexyl)pyridine, 4-(1-hexyl)pyridine,4-(1-octyl)pyridine, 4-(1-nonyl)pyridine, 4-(5-nonyl)pyridine,4-(1-decyl)pyridine, 4-dimethylaminopyridine,4-[di(n-hexyl)amino]pyridine, picolinic acid andpyridine-2,6-dicarboxylic acid is exemplified. As nitrogen-containingaromatic N-oxide compound, the compound in which a nitrogen atomcomposed of the aromatic ring of the above-mentioned nitrogen-containingaromatic compound is oxidized such as pyridine N-oxide compounds such aspyridine N-oxide is exemplified.

The amount of at least one compound selected from tertiary aminecompound, tertiary amine oxide compound, nitrogen-containing aromaticcompound and nitrogen-containing aromatic N-oxide compound to be used isusually 0.8 to 3 moles, preferably 0.9 to 1.2 moles per 1 mole of metalcompound in terms of the metal.

As hydrogen peroxide (c), an aqueous hydrogen peroxide solution which isan aqueous solution is usually used and a solution of hydrogen peroxidein an organic solvent may be used. It is preferred to use an aqueoushydrogen peroxide solution from the viewpoint of easy handling. Theconcentration of hydrogen peroxide in an aqueous hydrogen peroxidesolution or in a solution of hydrogen peroxide in an organic solvent isnot particularly limited, but in view of volume efficacy and safety, theconcentration is practically 1 to 60% by weight. As an aqueous hydrogenperoxide solution, a commercially available aqueous hydrogen peroxidesolution is usually used as it is, or if necessary, it may be used byappropriately adjusting the concentration by dilution or concentration.In addition, as a solution of hydrogen peroxide in an organic solvent, asolution prepared by extracting an aqueous hydrogen peroxide solutionwith an organic solvent, or distilling an aqueous hydrogen peroxidesolution in the presence of an organic solvent, may be used.

The amount of hydrogen peroxide to be used is usually 3 moles or more,preferably 5 moles or more relative to 1 mole of the metal or metalcompound in terms of the metal, and the upper limit of the amount is notparticularly defined.

Examples of the phosphate compound (D) include phosphoric acid; alkalimetal phosphate such as trisodium phosphate, tripotassium phosphate,disodium hydrogenphosphate, dipotassium hydrogenphosphate, sodiumdihydrogenphosphate and potassium dihydrogenphosphate; and alkalineearth metal phosphate such as calcium pyrophosphate and magnesiumphosphate. Among them, there are phosphates having hydrates and thehydrates may be used. The amount of the phosphate compound to be used isusually 0.2 mole or more per 1 mole of the metal or metal compound interms of the metal. Although there is no upper limited particularly, itis usually 1 mole or less.

The metal catalyst of the present invention is prepared by contactingand mixing the above-mentioned catalyst component compounds of (A) to(D). The mixing order is not limited particularly, but it is preferredto mix (A) with (C), followed by adding (D) to the mixture and thenadding (B) thereto.

The preparation of the metal catalyst may be carried out without using asolvent and may be carried out in the presence of a solvent. Examples ofthe solvent include an organic solvent such as an ether solvent such asdiethyl ether, methyl tert-butyl ether and tetrahydrofuran; an estersolvent such as ethyl acetate; a tertiary alcohol solvent such astert-butanol; a nitrile solvent such as acetonitrile and propionitrile;a halogenated hydrocarbon solvent such as dichloromethane; or in amixture of the organic solvent and water. The preparation temperature ofthe metal catalyst is usually −10 to 100° C.

By contacting and mixing the above-mentioned four components, theprepared liquid containing the metal catalyst is obtained, and forexample, the metal catalyst can be isolated by subjecting the preparedliquid as it is or, after adjusting a pH of the prepared liquid toneutral to acidic, to concentration. Further, the metal catalyst (or asthe metal complex) can be also isolated by, if necessary, addition ofwater and/or a water-insoluble organic solvent to the prepared liquid asit is or after adjusting a pH thereof, followed by extraction andconcentration of the resulting organic layer. The metal catalyst issometimes precipitated in the preparation solution depend on theconditions, and in that case, the metal catalyst may be isolated byfiltering the preparation solution. Examples of the water-insolubleorganic solvent include, for example, an aromatic hydrocarbon solventsuch as toluene and xylene; an ether solvent such as tert-butyl ether;and a halogenated hydrocarbon solvent such as dichloromethane.

Next, use of the obtained metal catalyst will be illustrated. The metalcatalyst has an oxidation catalytic activity and by reacting an olefinwith hydrogen peroxide in the presence of the above-mentioned metalcatalyst, an epoxide, a β-hydroxyhydroperoxide compound or a carbonylcompound can be produced.

First, a method for producing the epoxide by reacting the olefin withhydrogen peroxide using the metal catalyst in a pH range of 2 or moreand 4 or less will be illustrated.

The amount of the metal catalyst to be used is usually 0.001 to 0.95mole, preferably 0.005 to 0.1 mole in terms of the metal per 1 mole ofthe olefin.

The olefin compound is not particularly limited as far as it is acompound having one or more olefinic carbon-carbon double bond withinthe molecule. For example, the substituents represented by R₁, R₂, R₃and R₄ bound to two carbon atoms formed the double bond in the formula(1) represented in the following scheme is same or different, and theyindependently include a substituted or unsubstituted alkyl group, asubstituted or unsubstituted aryl group, a substituted or unsubstitutedaralkyl group, a substituted silyl group and a halogen atom other than ahydrogen atom.

Examples of the unsubstituted alkyl group include a straight, branchedor cyclic C1-10 alkyl group such as a methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl,n-octyl, isooctyl, n-nonyl, n-decyl, cyclopentyl and cyclohexyl group.

Examples of the substituted alkyl group include an alkoxy group(typically, C1-4 alkoxy group) such as a methoxy, ethoxy, n-propoxy,isopropoxy and n-butoxy group; a silyl group substituted with ahydrocarbon radical(s) (for example, the group selected from an alkylgroup (C1-4 alkyl group such as a methyl, ethyl, propyl and butyl group)and an aryl group (for example, a phenyl or naphthyl group); further, astraight, branched or cyclic alkyl group (typically, a straight,branched or cyclic C1-10 alkyl group) substituted with a halogen atomsuch as a fluorine, chlorine and bromine atom.

Examples of the unsubstituted aryl group include a phenyl and naphthylgroup. Examples of the substituted aryl group include an aryl groupsubstituted with an alkyl group (for example, C1-10 alkyl group like theabove), an alkoxy group (for example, C1-4 alkoxy group like the above),an alkylenedioxy group (for example, a C1-2 alkylenedioxy group such asa methylenedioxy and ethylenedioxy group), a silyl group substitutedwith a hydrocarbon radical(s) (for example, a silyl group substitutedwith the group selected from the alkyl and aryl group like the above), ahalogen atom like the above, or an acyl group (typically, a C2-4 acylgroup) such as an acetyl and propionyl group. Specifically examplesthereof include a 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl,2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl,2-methylphenyl, 4-methylphenyl, 4-methoxyphenyl and 4-acetylphenylgroup.

As the substituted or unsubstituted aralkyl group, the groups composedof the above-mentioned substituted or unsubstituted alkyl group and theabove-mentioned substituted or unsubstituted aryl group is exemplified.Specific examples thereof include a benzyl, phenylethyl, 4-fluorobenzyl,4-methoxybenzyl and 2-chlorobenzyl group.

Examples of the silyl group substituted with a hydrocarbon radical(s)include a silyl group substituted with a phenyl group(s) or a C1-4 alkylgroup(s) such as a trimethylsilyl, triethylsilyl, dimethylphenylsilyland methyldiphenylsilyl group.

Examples of the halogen atom include a fluorine, chlorine and bromineatom.

Alternatively, the substituent or unsubstituted alkyl groups bonded tocarbon atoms composed of the olefinic carbon-carbon double bond may bebonded each other at the terminal together with the carbon atom formedthe double bond to form a ring structure. Specific examples of the ringstructure include a C4-12 cycloalkane ring such as a cyclobutane ring, acyclopentane ring, a cyclohexane ring, a cycloheptane ring, acyclooctane ring, a cyclononane ring, a cyclodecane ring, acycloundecane ring and a cyclododecane ring, and a cycloalkane ringsubstituted with an alkyl group (for example, C1-10 alkyl group like theabove), an alkoxy group (for example, C1-4 alkoxy group like the above),a silyl group substituted with hydrocarbon radicals (for example, asilyl group substituted with the groups selected from aryl and alkylgroups like the above) or a halogen atom (for example, a fluorine,chlorine, bromine and iodine atom).

As the olefin, for example, a mono-substituted olefin represented by theformula (1a): R¹HC═CH₂ in which R², R³ and R⁴ are hydrogen atoms in theolefin compound of the formula (1) is exemplified. Meanwhile, in thepresent description, the mono-substituted olefin is defined includingethylene in which R¹ is a hydrogen atom. Specific examples of themono-substituted olefin include ethylene, propylene, 1-butene,1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-octadecene, 3,3-dimethyl-1-butene,vinylcyclopentane, vinylcyclohexane, allylcyclohexane, styrene,4-(tert-butyl)styrene, allylbenzene, 4-methoxystyrene, safrole, eugenoland 3,4-dimethoxy-1-allylbenzene.

Alternatively, as the olefin, for example, a di-substituted olefinrepresented by the formula (1b): R¹HC═CHR³, wherein R¹ and R³ representthe substituents like the above other than a hydrogen atom, or theformula (1c): R¹R²C═CH₂, wherein R¹, R² and R³ represent thesubstituents like the above other than a hydrogen atom, in which R² andR⁴ or R³ and R⁴ are hydrogen atoms in the olefin compound of the formula(1) is exemplified.

Specific examples of the di-substituted olefin include 2-butene,isobutylene, 2-methyl-1-butene, 2-pentene, 2-hexene, 2-methyl-1-hexene,3-hexene, 2-heptene, 2-methyl-1-heptene, 3-heptene, 2-octene, 3-octene,4-octene, 2-nonene, 2-methyl-2-nonene, 3-nonene, 4-nonene, 5-decene,2-methyl-1-undecene, cyclopentene, cyclohexene, 4-methylcyclohexene,cycloheptene, cyclooctene, cyclodecene, cyclododecene,methylenecyclohexane, β-methylstyrene, stilbene, isosafrole, isoeugenol,β-pinene and norbornene.

Further, a tri-substituted olefin represented by the formula (1d):R¹R²C═CHR³, wherein R⁴ is a hydrogen atom and R¹ to R³ represent thesubstituents like the above other than a hydrogen atom in the formula(1) is exemplified. Specific examples of the tri-substituted olefininclude 2-methyl-2-butene, 2-methyl-2-pentene, 2-methyl-2-hexene,2,5-dimethyl-2,4-hexadiene, 2-methyl-2-heptene, 1-methylcyclopentene,1-methylcyclohexene, 1-(tert-butyl)-cyclohexene, 1-isopropylcyclohexene,2-carene, 3-carene and α-pinene.

A tetra-substituted olefin wherein R¹ to R⁴ represent the substituentslike the above other than a hydrogen atom in the formula (1) isexemplified. Specific examples thereof include 2,3-dimethyl-2-butene and2,3,4-trimethyl-2-pentene.

Among the olefins, there are compounds having geometric isomers oroptical isomers. In the present invention, geometric isomers oroptically isomers alone may be used and a mixture of geometric isomersor a mixture of optical isomers may be used.

Hydrogen peroxide is usually used as an aqueous solution and a solutionof hydrogen peroxide in an organic solvent may be used. It is preferredto use an aqueous hydrogen peroxide solution from the viewpoint of easyhandling. The concentration of hydrogen peroxide in an aqueous hydrogenperoxide solution or in a solution in an organic solvent is notparticularly limited, but considering volume efficacy and safety, theconcentration is practically 1 to 60% by weight. As an aqueous hydrogenperoxide solution, usually, a commercially available aqueous hydrogenperoxide solution may be used as it is, or if necessary, after adjustingthe concentration of hydrogen peroxide thereof by dilution,concentration, and the like. A solution of hydrogen peroxide in anorganic solvent, for example, can be prepared by means of extraction ofan aqueous hydrogen peroxide solution with an organic solvent, ordistillation of an aqueous hydrogen peroxide solution in the presence ofan organic solvent.

The amount of hydrogen peroxide to be used is usually 0.8 mole or more,preferably 1 mole or more per 1 mole of the olefin. There is no upperlimit particularly, but it is usually about 5 moles or less, preferablyabout 3 moles or less per 1 mole of the olefin.

The reaction of the olefin and hydrogen peroxide may be carried outwithout using a solvent, and may be carried out in water or an organicsolvent. Examples of the organic solvent include an ether solvent suchas diethyl ether, methyl tert-butyl ether, tetrahydrofuran and diglyme;an ester solvent such as ethyl acetate; a tertiary alcohol solvent suchas tert-butanol; a nitrile solvent such as acetonitrile andpropionitrile; and a hydrocarbon solvent such as toluene, benzene,xylene and hexane. The amount of the solvent to be used is notparticularly limited.

The reaction is carried out by contacting the metal catalyst, the olefinand hydrogen peroxide in a pH range of 2 or more and 4 or less.Therefore, if necessary, the reaction may be carried out by adjustingthe pH of the reaction mixture into the above-mentioned range using acidor alkali.

The reaction temperature is usually −10 to 130° C. The reaction may beusually carried out under ordinary pressure conditions, and may becarried out under reduced pressure conditions or pressurized conditions.

The epoxide is produced with the progress of the reaction, and theprogress of the reaction can be confirmed by a conventional analyticalmeans such as gas chromatography, high performance liquidchromatography, thin layer chromatography, NMR and IR.

After completion of the reaction, the desired epoxide can be isolated bysubjecting the reaction mixture as it is or, if necessary, afterdegrading remaining hydrogen peroxide with a reducing agent such assodium sulfite, to concentration, crystallization, or the like. Further,the epoxide can be also isolated by, if necessary, addition of waterand/or a water-insoluble organic solvent to the reaction mixture,followed by extraction and concentration of the resulting organic layer.The isolated epoxide may be further purified by conventionalpurification means such as distillation, column chromatography andrecrystallization.

Examples of thus obtained epoxide include, for example, the epoxide ofthe following formula (I). Specific examples thereof include ethyleneoxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxypentane,4,4-dimethyl-1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane,1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane,1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane,1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane,3,3-dimethyl-1,2-epoxybutane, cyclopentylethylene oxide,cyclohexylethylene oxide, 3-cyclohexyl-1,2-epoxypropane, styrene oxide,4-(tert-butyl)styrene oxide, 3-phenyl-1,2-epoxypropane, 4-methoxystyreneoxide, safrole oxide, 3-(4-hydroxy-3-methoxyphenyl)-1,2-epoxypropane,3-(3,4-dimethoxyphenyl)-1,2-epoxypropane, 2,3-epoxybutane,2-methyl-1,2-epoxypropane, 2-methyl-1,2-epoxybutane, 2,3-epoxypentane,2,3-epoxyhexane, 2-methyl-1,2-epoxyhexane, 3,4-epoxyhexane,2,3-epoxyheptane, 3,4-epoxyheptane, 2,3-epoxyoctane, 3,4-epoxyoctane,4,5-epoxyoctane, 2,3-epoxynonane, 2-methyl-1,2-epoxynonane,3,4-epoxynonane, 4,5-epoxynonane, 5,6-epoxydecane,2-methyl-1,2-epoxyundecane, cyclopetene oxide, cyclohexene oxide,4-methylcyclohexene oxide, cycloheptene oxide, cyclooctene oxide,cyclodecene oxide, cyclododecene oxide, β-methylstyrene oxide, stilbeneoxide, isosafrole oxide, 1-(4-hydroxy-3-methoxyphenyl)-1,2-epoxypropane,β-pinene oxide, norbornene oxide, 2-methyl-2,3-epoxybutane,2-methyl-2,3-epoxypentane, 2-methyl-2,3-epoxyhexane,2,5-dimethyl-2,3-epoxyhex-4-ene, 2-methyl-2,3-epoxyheptane,1-methyl-1,2-epoxycyclopentane, 1-methyl-1,2-epoxycyclohexane,1-(tert-butyl)-1,2-epoxycyclohexane, 1-isopropyl-1,2-epoxycyclohexane,2-carene oxide, 3-carene oxide, α-pinene oxide,2,3-dimethyl-2,3-epoxybutane and 2,3,4-trimethyl-2,3-epoxypentane.

Then, a method for producing a β-hydroxyhydroperoxide compound or acarbonyl compound by reacting an olefin with hydrogen peroxide in a pHrange of 0 or more and less than 2 in the presence of the metal catalystwill be illustrated.

Examples of the olefin include the compounds as described above.Depending on the reaction conditions and the type of substitution, theβ-hydroxyhydroperoxide compound or the carbonyl compound such as thealdehyde, the ketone and the carboxylic acid. The β-hydroxyhydroperoxidecompound can be obtained preferably by carrying out the reaction in anorganic solvent or under absolute conditions. Examples of the method forcarrying out the reaction under absolute conditions include, forexample, a method for carrying out in the presence of a dehydratingagent in a reaction system. Examples of the dehydrating agent includeanhydrous magnesium sulfate, anhydrous sodium sulfate, boric anhydride,polyphosphoric acid and diphosphorus pentaoxide. As the amount of thedehydrating agent to be used, the amount of the dehydrating agent thatcan remove water in the reaction system is enough.

The reaction temperature is usually 0 to 200° C. Theβ-hydroxyhydroperoxide compound and the aldehyde can be obtainedpreferably when the reaction temperature is less than 65° C. The ketoneand the carboxylic acid can be obtained preferably when the reactiontemperature is 65° C. or more.

When the mono-substituted olefin is used as the olefin, theβ-hydroxyhydroperoxide compound or the carbonyl compound such as thealdehyde and the carboxylic acid preferably are obtained by selectingappropriately the reaction conditions like the above.

For example, the β-hydroxyhydroperoxide compound wherein three groupsamong R¹ to R⁴ are hydrogen atoms in the formula (II) is obtained mainlyby reacting the mono-substituted olefin of the formula (1a) withhydrogen peroxide preferably in the organic solvent or under absoluteconditions, more preferably at 0° C. to less than 45° C. in addition tothe above-mentioned conditions.

For example, the aldehyde represented by R¹CHO is obtained mainly byreacting the mono-substituted olefin of the formula (1a) with hydrogenperoxide preferably at 45° C. to less than 60° C.

For example, the carboxylic acid represented by R¹—COOH is obtainedmainly by reacting the mono-substituted olefin of the formula (1a) withhydrogen peroxide preferably at 65° C. or more, more preferably at lessthan 200° C.

When 1-hexene, for example, is used as the mono-substituted olefin,2-hydroperoxy-1-hydroxyhexane and/or 1-hydroperoxy-2-hydroxyhexane,pentanal and pentanoic acid are obtained.

For example, the β-hydroxyhydroperoxide compound wherein R¹ and R² arehydrogen atoms in the formula (II) is obtained mainly by reacting thedi-substituted terminal olefin of the formula (1c) with hydrogenperoxide preferably in the organic solvent or under absolute conditions,more preferably at 0° C. to less than 45° C. in addition to theabove-mentioned conditions.

Also, for example, the ketone represented by the formula (IIIa) isobtained mainly by reacting the di-substituted terminal olefin of theformula (1c) with hydrogen peroxide preferably at 65° C. or more.

When α-methylstyrene, for example, is used as the di-substitutedterminal olefin, 2-hydroperoxy-2-phenyl-1-propanol and acetophenone areobtained. When methylenecyclohexane, for example, is used,1-hydroperoxy-1-hydroxymethylcyclohexane and cyclohexanone are obtained.

When a di-substituted internal olefin is used as the olefin, aβ-hydroxyhydroperoxide compound, an aldehyde and a carboxylic acid areobtained.

For example, the β-hydroxyhydroperoxide compound wherein R² and R⁴ arehydrogen atoms in the formula (II) is obtained mainly by reacting thedi-substituted internal olefin of the formula (1b) with hydrogenperoxide preferably in the organic solvent or under absolute conditions,more preferably at 0° C. to less than 45° C. in addition to theabove-mentioned conditions.

Alternatively, for example, the aldehydes represented by R¹CHO and R³CHOare obtained mainly by reacting the di-substituted internal olefin ofthe formula (1b) with hydrogen peroxide preferably at 45° C. to lessthan 65° C.

Alternatively, for example, the carboxylic acids represented by R¹COOHand R³COOH are obtained mainly by reacting the di-substituted internalolefin of the formula (1b) with hydrogen peroxide preferably at 65° C.or more.

When cyclopentene, for example, is used as the di-substituted internalolefin, 1-hydroperoxy-2-hydroxycyclopentane, glutaraldehyde and glutaricacid are obtained. When 2-hexene, for example, is used,2-hydroperoxy-3-hydroxyhexane and/or 3-hydroperoxy-2-hydroxyhexane,butanal, butanoic acid, acetaldehyde and acetic acid are obtained.

When a tri-substituted olefin is used as the olefin, theβ-hydroxyhydroperoxide compound, the ketone, the aldehyde and thecarboxylic acid.

For example, the β-hydroxyhydroperoxide compound wherein R⁴ is ahydrogen atom in the formula (II) is obtained mainly by reacting thetri-substituted olefin of the formula (1d) with hydrogen peroxidepreferably in the organic solvent or under absolute conditions, morepreferably at 0° C. to less than 45° C. in addition to theabove-mentioned conditions.

Alternatively, for example, the ketone and the aldehyde represented byR¹R²C═O and R³CHO are obtained mainly by reacting the tri-substitutedolefin of the formula (1d) with hydrogen peroxide preferably at 45° C.to less than 65° C.

Alternatively, for example, the carboxylic acid represented by R¹R²C═Oand R³COOH are obtained mainly by reacting the tri-substituted olefin ofthe formula (1d) with hydrogen peroxide preferably at 65° C. or more.

When 2-methyl-2-pentene, for example, is used as the tri-substitutedolefin, 2-methyl-2-hydroperoxy-3-hydroxypentane, acetone,propionaldehyde and propionic acid are obtained.

When a tetra-substituted olefin is used as the olefin, theβ-hydroxyhydroperoxide compound and the ketone are obtained.

For example, the β-hydroxyhydroperoxide compound of the formula (II) isobtained mainly by reacting the tetra-substituted olefin of the formula(1), provided that wherein R¹ to R⁴ are not hydrogen atoms, withhydrogen peroxide preferably in the organic solvent or under absoluteconditions, more preferably at 0° C. to less than 45° C. in addition tothe above-mentioned conditions.

Alternatively, for example, the ketones represented by R¹R²C═O andR³R⁴C═O, provided that wherein R¹ to R⁴ are not hydrogen atoms, areobtained mainly by reacting the tetra-substituted olefin of the formula(1) with hydrogen peroxide preferably at 65° C. or more.

When 2,3-dimethyl-2-butene, for example, is used as thetetra-substituted olefin, 2,3-dimethyl-2-hydroperoxy-3-hydroxybutane andacetone are obtained.

Hydrogen peroxide is also usually used as an aqueous solution like theabove and a solution of hydrogen peroxide in an organic solvent may beused. The amount of hydrogen peroxide to be used is usually 1 mole ormore per 1 mole of the olefin. There is no upper limit particularly, butit is usually 10 moles or less per 1 mole of the olefin.

The amount of the metal complex to be used is usually 0.001 to 0.95mole, preferably 0.005 to 0.1 mole as the metal per 1 mole of theolefin.

The reaction may be carried out without using a solvent, and may becarried out in water or an organic solvent. Examples of the organicsolvent include the solvents as the above.

Since the present reaction is carried out by contacting the olefin andhydrogen peroxide in a pH range of 0 or more to less than 2 in thepresence of the metal catalyst, the reaction may be carried out, ifnecessary, by adjusting the pH of the reaction mixture to theabove-mentioned range using acid or alkaline.

The carbonyl compound is produced with the progress of the reaction, andthe progress of the reaction can be confirmed by a conventionalanalytical means such as gas chromatography.

After completion of the reaction, the carbonyl compound can be isolatedby subjecting the reaction mixture as it is or, if necessary, afterdegrading remaining hydrogen peroxide with a reducing agent such assodium sulfite, to concentration, crystallization, and the like.Further, the carbonyl compound can be also isolated by, if necessary,addition of water and/or a water-insoluble organic solvent to thereaction mixture, followed by extraction and concentration of theresulting organic layer. The isolated carbonyl compound may be furtherseparated or purified by conventional purification means such asdistillation, column chromatography and recrystallization.

Examples of thus obtained β-hydroxyhydroperoxide compound include1-hydroxy-2-hydroperoxyhexane, 2-hydroxy-1-hydroperoxyhexane,1-hydroxy-2-hydroperoxyheptane, 2-hydroxy-1-hydroperoxyheptane,1-hydroxy-2-hydroperoxyoctane, 2-hydroxy-1-hydroperoxyoctane,1-hydroxy-2-hydroperoxydodecane, 2-hydroxy-1-hydroperoxydodecane,1-hydroxy-2-phenyl-2-hydroperoxyethane,1-hydroxy-2-(4-methylphenyl)-2-hydroperoxyethane,1-hydroxy-2-hydroperoxy-3-phenylpropane,2-hydroxy-1-hydroperoxy-3-phenylpropane,1-hydroxy-2-hydroperoxy-3-(4-methoxyphenyl)propane and2-hydroxy-1-hydroperoxy-3-(4-methoxyphenyl)propane.

Examples of thus obtained carbonyl compound include an aldehyde such asformaldehyde, acetaldehyde, propionaldehyde, butylaldehyde,pentylaldehyde, hexylaldehyde, heptylaldehyde, decylaldehyde,undecanylaldehyde, benzaldehyde, 5-oxohexylaldehyde,2-methyl-5-oxohexylaldehyde, 4-methyl-5-oxohexylaldehyde,3-methyl-5-oxohexylaldehyde, 2,4-dimethyl-5-oxohexylaldehyde,3,4-dimethyl-5-oxohexylaldehyde, 2,3-dimethyl-5-oxohexylaldehyde,2,3,4-trimethyl-5-oxohexylaldehyde, 6-oxoheptylaldehyde,2-methyl-6-oxoheptylaldehyde, 4-methyl-6-oxoheptylaldehyde,2,4-dimethyl-6-oxoheptylaldehyde, 2,3-dimethyl-6-oxoheptylaldehyde,3,4-dimethyl-6-oxoheptylaldehyde, 2,3,4-trimethyl-6-oxoheptylaldehyde,glutaraldehyde, adipaldehyde, heptanedialdehyde, octanedialdehyde,2-chloroglutaraldehyde, 2-methylglutaraldehyde, 3-methylglutaraldehydeand 2,3-dimethylglutaraldehyde,

a ketone such as acetone, methyl ethyl ketone, diethyl ketone,2-pentanone, 4,4-dimethylpentan-2-one, diethyl ketone, methyl propylketone, acetophenone, cyclobutanone, cyclopentanone, cyclohexanone,benzophenone, nopinone, 1,3,3-trimethylindolinone, 2,6-heptanedione,2,7-octanedione, 1,6-cyclodecanedione, 4-acetoxyacetophenone,2-methoxy-6-(propan-2-one)acetophenone,2-carboethoxy-3-methylcyclopentanone and benzophenone, and a carboxylicacid such as formic acid, acetic acid, propionic acid, butanoic acid,pentanoic acid, hexanoic acid, heptanoic acid, benzoic acid,4-methylbenzoic acid, phenylacetic acid, (4-methoxyphenyl)acetic acid,chloroacetic acid, ethoxyacetic acid, benzyloxyacetic acid,3,3-dimethyl-2-carbomethoxycyclopropanecarboxylic acid,3,3-dimethyl-2-carboethoxycyclopropanecarboxylic acid, glutaric acid,adipic acid, pimelic acid, suberic acid, 2-methylglutaric acid,3-methylglutaric acid, 3-chloroglutaric acid, 2,3-dimethylglutaric acid,2,4-dimethylglutaric acid, 2-methyladipic acid, 3-methyladipic acid,2,3-dimethyladipic acid, 2,4-dimethyladipic acid, 3,4-dimethyladipicacid, 2,3,4-trimethylglutaric acid, cyclopentane-1,3-dicarboxylic acid,biphenyl-2,2′-dicarboxylic acid, butane-1,2,3,4-tetracarboxylic acid,1-(carboxymethyl)cyclopentane-2,3,4-tricarboxylic acid, homophthalicacid and cyclopentane-1,2,3,4-tetracarboxylic acid.

Next, a method for producing a corresponding carbonyl compound byreacting a primary or secondary alcohol and hydrogen peroxide using themetal catalyst of the present invention will be illustrated.

As the primary or secondary alcohol, the formula (2): R⁵R⁶CH—OH, whereinR⁵ represents a substituted or unsubustituted alkyl group; a substitutedor unsubstituted aryl group; a substituted or unsubstituted aralkylgroup; or a silyl group substituted with hydrocarbon radicals, and R⁶represents a substituted or unsubustituted alkyl group; a substituted orunsubstituted aryl group; a substituted or unsubstituted aralkyl group;a silyl group substituted with hydrocarbon radicals; or a hydrogen atom,are exemplified specifically.

The group represented by R⁵ or R⁶ will be illustrated below.

Examples of the unsubstituted alkyl group include a straight, branchedor cyclic C1-8 alkyl group such as a methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl,isooctyl, n-nonyl, n-decyl, cyclopentyl and cyclohexyl group. Examplesof the substituted alkyl group include an alkyl group substituted withan alkoxy group such as a methoxy, ethoxy, n-propoxy, isopropoxy andn-butoxy group; a silyl group such as a trimethylsilyl group; or ahalogen atom such as a fluorine, chlorine and bromine atom.

Specific examples of the substituted alkyl group include amethoxymethyl, ethoxymethyl, methoxyethyl, trimethylsilylmethyl,fluoromethyl, chloromethyl, bromomethyl and trifluoromethyl group.

Examples of the unsubstituted aryl group include a phenyl and naphthylgroup. Examples of the substituted aryl group include the aryl groupsubstituted with, for example, the above-mentioned alkyl group; theabove-mentioned alkoxy group; the above-mentioned silyl group; theabove-mentioned halogen atom; or an acyl group such as an acetyl andpropionyl group. Examples of thus substituted aryl group include a2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl,3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 2-methylphenyl,4-methylphenyl, 4-methoxyphenyl and 4-acetylphenyl group.

As the substituted or unsubstituted aralkyl group, the group composed ofthe above-mentioned substituted or unsubstituted alkyl group and theabove-mentioned substituted or unsubstituted aryl group. Specificexamples thereof include a benzyl, phenylethyl, 4-fluorobenzyl,4-methoxybenzyl and 2-chlorobenzyl group.

Examples of the silyl group substituted hydrocarbon radicals include asilyl group substituted with the group selected from alkyl groups andaryl groups such as a trimethylsilyl, triethylsilyl, dimethylphenylsilyland methyldiphenylsilyl group.

Specific examples thereof include a primary alcohol such as ethanol,1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol,1-nonanol, 1-decanol, 2-methyl-1-hexanol, 4-methyl-1-hexanol,2,2-dimethyl-1-propanol, 1,6-hexanediol, benzyl alcohol, 2-fluorobenzylalcohol, 3-fluorobenzyl alcohol, 4-fluorobenzyl alcohol, 2-chlorobenzylalcohol, 3-chlorobenzyl alcohol, 4-chlorobenzyl alcohol, 2-bromobenzylalcohol, 3-bromobenzyl alcohol, 4-bromobenzyl alcohol, 2-methylbenzylalcohol, 3-methylbenzyl alcohol, 4-methylbenzyl alcohol, 4-methoxybenzylalcohol, 2-phenylethanol, 2-(2-fluorophenyl)ethanol,2-(3-fluorophenyl)ethanol, 2-(4-fluorophenyl)ethanol,2-(2-chlorophenyl)ethanol, 2-(2-bromophenyl)ethanol,2-(4-methoxyphenyl)ethanol and 2-(4-acetylphenyl)ethanol.

Further, for example, a secondary alcohol such as 2-propanol, 2-butanol,2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2-heptanol, 3-heptanol,4-heptanol, 2-octanol, 3-octanol, 4-octanol, 2-nonanol, 3-nonanol,4-nonanol, 5-nonanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol,cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol,cyclododecanol, 2-methylcyclohexanol, 3-methylcyclohexanol,4-methylcyclohexanol, 2-tert-butylcyclohexanol,3-tert-butylcyclohexanol, 4-tert-butylcyclohexanol, 1-phenylethanol,1-(2-fluorophenyl)ethanol, 1-(3-fluorophenyl)ethanol,1-(4-fluorophenyl)ethanol, 1-(2-chlorophenyl)ethanol,1-(2-bromophenyl)ethanol, 1-(4-methoxyphenyl)ethanol,1-(4-acetylphenyl)ethanol and α-trimethylsilylbenzyl alcohol isexemplified.

When the primary alcohol (for example, when R⁶ represents a hydrogenatom in the formula (2)) is used, an aldehyde (for example, R⁵CHO) and acarboxylic acid (for example, R⁵COOH) are obtained. When 1-butanol isused as the primary alcohol for example, butylaldehyde and/or butanoicacid are obtained.

When the secondary alcohol (for example, when R⁶ is not a hydrogen atomin the formula (2)) is used, a ketone (for example, R⁵COR⁶) is obtained.When 1-phenylethanol is used as the secondary alcohol for example,acetophenone is obtained.

Hydrogen peroxide is also usually used as an aqueous solution like theabove and a solution of hydrogen peroxide in an organic solvent may beused. The amount of hydrogen peroxide to be used may be set for to thealcohol to be used and the desired carbonyl compound as below.

When the primary alcohol is used and the aldehyde is desired, the amountof hydrogen peroxide to be used is usually 0.9 to 1.5 moles per 1 moleof the alcohol. When the primary alcohol is used and the carboxylic acidis desired, the amount of hydrogen peroxide to be used is usually 1.5moles or more per 1 mole of the alcohol. There is no upper limitparticularly, but it is usually 10 moles or less per 1 mole of thealcohol.

When the secondary alcohol is used and the ketone is desired, the amountof hydrogen peroxide to be used is usually 0.9 mole or more per 1 moleof the alcohol. There is no upper limit particularly, but it is usually10 moles or less per 1 mole of the alcohol.

The amount of the metal catalyst to be used is usually about 0.001 to0.95 mole, preferably about 0.005 to 0.1 mole as the metal per 1 mole ofthe primary or secondary alcohol.

The reaction may be carried out without using a solvent, and may becarried out in water or an organic solvent. Examples of the organicsolvent include the solvents as same as those exemplified as thesolvents used for producing the epoxides.

The present reaction is carried out by contacting the metal catalyst,the primary or secondary alcohol and hydrogen peroxide. The mixing orderis not particularly limited.

The reaction temperature is usually in a range of about 0 to 200° C.

A carbonyl compound is produced with the progress of the reaction, andthe progress of the reaction can be also confirmed by a conventionalanalytical means such as gas chromatography like the above.

After completion of the reaction, the carbonyl compound can be isolatedby subjecting the reaction mixture as it is or, if necessary, afterdegrading remaining hydrogen peroxide with a reducing agent such assodium sulfite, to concentration, crystallization, and the like.Further, the carbonyl compound can be also isolated by, if necessary,addition of water and/or a water-insoluble organic solvent to thereaction mixture, followed by extraction and concentration of theresulting organic layer. The isolated carbonyl compound may be separatedor further purified, if necessary, by conventional means such asdistillation, column chromatography and recrystallization.

Examples of thus obtained carbonyl compound include acetaldehyde,propionaldehyde, butylaldehyde, pentylaldehyde, hexylaldehyde,heptylaldehyde, octylaldehyde, nonylaldehyde, decylaldehyde,2-methyl-1-hexylaldehyde, 2,2-dimethyl-1-propionaldehyde, adipaldehyde,benzaldehyde, 2-fluorobenzaldehyde, 3-fluorobenzaldehyde,4-fluorobenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde,4-chlorobenzaldehyde, 2-bromobenzaldehyde, 3-bromobenzaldehyde,4-bromobenzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde,4-methylbenzaldehyde, 4-methoxybenzaldehyde, 2-phenylacetaldehyde,2-(2-fluorophenyl)acetaldehyde, 2-(3-fluorophenyl)acetaldehyde,2-(4-fluorophenyl)acetaldehyde, 2-(2-chlorophenyl)acetaldehyde,2-(2-bromophenyl)acetaldehyde, 2-(4-methoxyphenyl)acetaldehyde and2-(4-acetylphenyl)acetaldehyde.

Examples of the carboxylic acid include, acetic acid, propionic acid,butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoicacid, nonanoic acid, decanoic acid, 2-methyl-1-hexanoic acid,4-methyl-1-hexanoic acid, 2,2-dimethyl-1-propionic acid, adipinic acid,benzoic acid, 2-fluorobenzoic acid, 3-fluorobenzoic acid,4-fluorobenzoic acid, 2-chlorobenzoic acid, 3-chlorobenzoic acid,4-chlorobenzoic acid, 2-bromobenzoic acid, 3-bromobenzoic acid,4-bromobenzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid,4-methylbenzoic acid, 4-methoxybenzoic acid, phenylacetic acid,(2-fluorophenyl)acetic acid, (3-fluorophenyl)acetic acid,(4-fluorophenyl)acetic acid, (2-chlorophenyl)acetic acid,(2-bromophenyl)acetic acid, (4-methoxyphenyl)acetic acid and(4-acetylphenyl)acetic acid.

Examples of the ketone include acetone, 2-butanone, 2-pentanone,3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone,4-heptanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone,4-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-decanone,cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone,cyclooctanone, cyclododecanone, 2-methylcyclohexanone,3-methylcyclohexanone, 4-methylcyclohexanone, 2-tert-butylcyclohexanone,3-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, acetophenone,o-fluoroacetophenone, m-fluoroacetophenone, p-fluoroacetophenone,o-chloroacetophenone, o-bromoacetophenone, o-methoxyacetophenone,p-methoxyacetophenone, p-methoxyacetophenone and benzoyltrimethylsilane.

A part of the embodiments of the method for producing of the presentinvention will be illustrated as scheme below.

EXAMPLES

The following Examples further illustrate the present invention indetail, but the present invention is not limited by these Examples. Gaschromatography was used for analysis.

Example 1

Into a 50 mL round-bottomed flask equipped with a reflux condenser, 0.92g of a tungsten metal powder and 3.96 g of a 30% by weight aqueoushydrogen peroxide were charged at room temperature, and the mixture wasstirred and maintained for 15 minutes to obtain a clear and colorlesshomogeneous solution. To the solution, 0.49 g of phosphoric acid wasadded and the resulting solution was stirred and maintained at roomtemperature for 2 hours. 2.92 g of tri(n-dodecyl)amine and 8 mL ofdichloromethane were added thereto and the resulting solution wasstirred and maintained at room temperature for 4 hours. Then, theresulting solution was subjected to separation treatment and theobtained organic layer was concentrated to obtain 4.02 g of yellow waxsolid tungsten complex. Yield 97% (based on the tungsten metal).

¹H-NMR(solvent: CDCl₃, based on TMS, unit: ppm) δ 0.88 (t, 9H, J=7.0Hz), 1.25-1.30 (m, 54H), 1.73 (br, 6H), 3.59 (br, 6H)

¹³C-NMR(solvent: CDCl₃, based on TMS, unit: ppm) δ 14.1, 22.7, 22.9,26.1, 29.4, 29.7, 31.9, 63.6

IR(neat, unit: cm⁻¹) 2956, 2921, 2871, 2853, 1546, 1466, 1403, 1378,1315, 1262, 1072, 1035, 941, 888, 848, 767, 751, 721, 678, 644

elementary analysis value: C, 54.4; H, 9.8; N, 1.6; P, 0.95.

Example 2

Into a 50 mL round-bottomed flask equipped with a reflux condenser, 0.88g of a tungsten metal powder, 4 g of water and 3.96 g of a 30% by weightaqueous hydrogen peroxide were charged at room temperature, and themixture was stirred and maintained for 15 minutes to obtain a clear andcolorless homogeneous solution. To the solution, 0.56 g of phosphoricacid was added and the resulting solution was stirred and maintained atroom temperature for 2 hours. 2.88 g of tri(n-dodecyl)amine N-oxide and10 mL of dichloromethane were added thereto and the resulting solutionwas stirred and maintained at room temperature for 4 hours. Then, theresulting solution was subjected to separation treatment and theobtained organic layer was concentrated to obtain 4.00 g of yellow waxsolid tungsten complex. Yield 100% (based on the tungsten metal).

¹H-NMR(solvent: CDCl₃, based on TMS, unit: ppm) δ 0.88 (t, 9H, J=7.0Hz), 1.25-1.30 (m, 54H), 1.73 (br, 6H), 3.59 (br, 6H)

¹³C-NMR(solvent: CDCl₃, based on TMS, unit: ppm) δ 14.1, 22.7, 22.9,26.1, 29.4, 29.7, 31.9, 63.6

IR(neat, unit: cm⁻¹) 2956, 2921, 2871, 2853, 1466, 1378, 1078, 1036,944, 888, 848, 772, 721, 678

elementary analysis value: C, 54.4; H, 9.7; N, 1.7; P, 1.41.

Example 3

Into a 50 mL round-bottomed flask equipped with a reflux condenser, 0.92g of a tungsten metal powder, 4 g of water and 3.96 g of a 30% by weightaqueous hydrogen peroxide were charged at room temperature, and themixture was stirred and maintained for 15 minutes to obtain a clear andcolorless homogeneous solution. To the solution, 0.58 g of phosphoricacid was added and the resulting solution was stirred and maintained atroom temperature for 2 hours. 1.77 g of tri(n-octyl)amine and 10 mL ofdiethyl ether were added thereto and the resulting solution was stirredand maintained at room temperature for 4 hours. Then, the resultingsolution was subjected to separation treatment and the obtained organiclayer was concentrated to obtain 3.20 g of yellow wax solid tungstencomplex. Yield 99% (based on the tungsten metal).

¹H-NMR(solvent: CDCl₃, based on TMS, unit: ppm) δ 0.89 (t, 9H, J=7.0Hz), 1.2-1.25 (m, 30H), 1.72 (br, 6H), 3.10 (br, 2H), 3.57 (br, 4H), 6.0(br, 2H)

¹³C-NMR(solvent: CDCl₃, based on TMS, unit: ppm) δ 14.0, 22.6, 23.2,26.0, 26.6, 28.9, 29.1, 29.2, 31.7, 52.8, 63.9

IR(neat, unit: cm⁻¹) 2956, 2926, 2856, 1458, 1376, 1086, 1034, 949, 891,845, 723, 677, 647

elementary analysis value: C, 42.3; H, 7.9; N, 2.0; P, 1.82.

Example 4

Into a 100 mL Schlenk tube equipped with a reflux condenser, 0.66 g ofthe tungsten complex obtained in the above-mentioned Example 1, 9.6 g ofa 30% by weight aqueous hydrogen peroxide, 0.1 g of a 20% by weightaqueous sodium hydroxide and a toluene solution containing 2.2 g of1-octene (used 4 mL of toluene) were charged at room temperature, andthe mixture was stirred for 6 hours at an inner temperature of 90° C. toeffect reaction. A pH value of the reaction mixture was about 3.5. Aftercompletion of the reaction, the reaction mixture was cooled to roomtemperature and subjected to separation treatment to obtain an organiclayer containing 1,2-epoxyoctane. Yield of 1,2-epoxyoctane was 84%(based on 1-octene).

Example 5

Into a 100 mL Schlenk tube equipped with a reflux condenser, 0.66 g ofthe tungsten complex obtained in the above-mentioned Example 1, 9.6 g ofa 30% by weight aqueous hydrogen peroxide and a toluene solutioncontaining 2.2 g of 1-octene (used 4 mL of toluene) were charged at roomtemperature, and the mixture was stirred for 6 hours at an innertemperature of 90° C. to effect reaction. A pH value of the reactionmixture was about 1.7. After completion of the reaction, the reactionmixture was cooled to room temperature and subjected to separationtreatment to obtain an organic layer containing heptanoic acid. Yield ofheptanoic acid was 84% (based on 1-octene).

Example 6

Into a 50 mL flask equipped with a reflux condenser, 66 mg of thetungsten complex obtained in the above-mentioned Example 2, 5.7 g of a30% by weight aqueous hydrogen peroxide and 980 mg of 1-heptene werecharged at room temperature, and the mixture was stirred for 6 hours atan inner temperature of 90° C. to effect reaction. After completion ofthe reaction, the reaction mixture was cooled to room temperature and,10 mL of diethyl ether was added thereto. The reaction mixture wassubjected to separation treatment to obtain an organic layer containinghexanoic acid. Yield of hexanoic acid was 60% (based on 1-heptene).1-heptene was recovered in 35%.

Example 7

Into a 50 mL flask equipped with a reflux condenser, 66 mg of thetungsten complex obtained in the above-mentioned Example 2, 3.4 g of a30% by weight aqueous hydrogen peroxide and 1.08 g of benzyl alcoholwere charged at room temperature, and the mixture was stirred for 6hours at an inner temperature of 90° C. to effect reaction. Aftercompletion of the reaction, the reaction mixture was cooled to roomtemperature and 10 mL of toluene was added thereto. The reaction mixturewas subjected to separation treatment to obtain an organic layercontaining benzoic acid. Yield of benzoic acid was 94% (based on benzylalcohol).

Example 8

Into a 50 mL flask equipped with a reflux condenser, 70 mg of thetungsten complex obtained in the above-mentioned Example 2, 1.37 g of a30% by weight aqueous hydrogen peroxide and 1.31 g of benzyl alcoholwere charged at room temperature, and the mixture was stirred for 2hours at an inner temperature of 80° C. to effect reaction. Aftercompletion of the reaction, the reaction mixture was cooled to roomtemperature and 10 mL of toluene was added thereto. The reaction mixturewas subjected to separation treatment to obtain an organic layercontaining benzaldehyde. Yield of benzaldehyde was 89% (based on benzylalcohol). Benzoic acid was formed as by-product in 10%.

Example 9

Into a 50 mL flask equipped with a reflux condenser, 60 mg of thetungsten complex obtained in the above-mentioned Example 3, 3.4 g of a30% by weight aqueous hydrogen peroxide and 1.02 g of 1-hexanol werecharged at room temperature, and the mixture was stirred for 6 hours atan inner temperature of 90° C. to effect reaction. After completion ofthe reaction, the reaction mixture was cooled to room temperature and 10mL of diethyl ether was added thereto. The reaction mixture wassubjected to separation treatment to obtain an organic layer containinghexanoic acid. Yield of hexanoic acid was 89% (based on 1-hexanol).

Example 10

Into a 50 mL flask equipped with a reflux condenser, 60 mg of thetungsten complex obtained in the above-mentioned Example 3, 3.4 g of a30% by weight aqueous hydrogen peroxide and 1.22 g of 1-phenethylalcohol were charged at room temperature, and the mixture was stirredfor 6 hours at an inner temperature of 90° C. to effect reaction. Aftercompletion of the reaction, the reaction mixture was cooled to roomtemperature and 10 mL of toluene was added thereto. The reaction mixturewas subjected to separation treatment to obtain an organic layercontaining acetophenone. Yield of acetophenone was 99% (based on1-phenethyl alcohol).

Example 11

Into a 50 mL round-bottomed flask equipped with a reflux condenser, 1.58g of sodium tungstate dihydrate, 4 g of water and 3.96 g of a 30% byweight aqueous hydrogen peroxide were charged at room temperature, andthe mixture was stirred and maintained for 15 minutes to obtain a clearand colorless homogeneous solution. To the solution, 1.66 g ofphosphoric acid was added and the resulting solution was stirred andmaintained at room temperature for 2 hours. 1.77 g of tri(n-octyl)amineand 10 mL of diethyl ether were added thereto and the resulting solutionwas stirred and maintained at room temperature for 4 hours. Then, theresulting solution was subjected to separation treatment and theobtained organic layer was concentrated to obtain 2.8 g of yellow waxsolid tungsten complex. Yield 88% (based on tungsten).

¹H-NMR(solvent: CDCl₃, based on TMS, unit: ppm) δ 0.89 (t, 9H, J=7.0Hz), 1.2-1.5 (m, 30H), 1.73 (br, 6H), 3.10 (br, 2H), 3.55 (br, 4H), 6.0(br, 2H)

¹³C-NMR(solvent: CDCl₃, based on TMS, unit: ppm) δ 14.0, 22.6, 23.2,26.0, 26.6, 28.9, 29.1, 29.2, 31.7, 52.6, 63.8

elementary analysis value: C, 45.6; H, 8.1; N, 2.2; P, 1.73.

Example 12

Into a 50 mL flask equipped with a reflux condenser, 60 mg of thetungsten complex obtained in the above-mentioned Example 11, 3.4 g of a30% by weight aqueous hydrogen peroxide and 1.08 g of benzyl alcoholwere charged at room temperature, and the mixture was stirred for 6hours at an inner temperature of 90° C. to effect reaction. Aftercompletion of the reaction, the reaction mixture was cooled to roomtemperature and 10 mL of toluene was added thereto. The reaction mixturewas subjected to separation treatment to obtain an organic layercontaining benzoic acid. Yield of benzoic acid was 94% (based on benzylalcohol).

Comparative Example 1

According a similar manner as that of Example 1, 4.13 g of pale yellowwax solid tungsten complex was obtained except that 0.49 g of phosphoricacid was not used.

IR(neat, unit: cm⁻¹) 2956, 2922, 2853, 1550, 1466, 1378, 1045, 977, 958,876, 815, 782, 720

INDUSTRIAL APPLICABILITY

According to the present invention, A metal catalyst is prepared bycontacting (A) at least one metal or metal compound selected from thegroup consisting of i) tungsten compounds composed of tungsten and anelement of group IIIb, IVb, Vb, or VIb, ii) molybdenum compoundscomposed of molybdenum and an element of group IIIb, IVb, Vb, or VIb;(B) at least one compound selected from the group consisting of tertiaryamine compounds, tertiary amine oxide compounds, nitrogen-containingaromatic compounds and nitrogen-containing aromatic N-oxide compounds;(C) hydrogen peroxide; and (D) a phosphate compound. Since an epoxide isobtained from olefin and hydrogen peroxide using the metal catalystwithout using a solvent having problems in the viewpoint of environmentand occupational safety and health such as chloroform as reactionsolvent, it is industrially advantageous. Further, since a carbonylcompound such as aldehyde wherein a carbon-carbon bond of an olefin isbroken oxidatively or a β-hydroxyhydroperoxide compound is obtained, itis useful industrially in this viewpoint, too.

1. A process for producing a β-hydroxyhydroperoxide compound or acarbonyl compound, which comprises: contacting (A) at least one metal ormetal compound selected from i) tungsten compounds composed of tungstenand an element of group IIIb, IVb, Vb, or VIb, ii) molybdenum compoundscomposed of molybdenum and an element of group IIIb, IVb, Vb, or VIb,and iii) tungsten metal and molybdenum metal; (B) at least one compoundselected from tertiary amine oxide compounds and nitrogen-containingaromatic N-oxide compounds; (C) hydrogen peroxide; and (D) a phosphatecompound, to obtain a metal catalyst and then reacting an olefin withhydrogen peroxide in the pH range of 0 or more and less than 2 in thepresence of said metal catalyst, wherein the carbonyl compound isproduced by oxidatively breaking a carbon-carbon bond of the olefin. 2.A process for producing a carbonyl compound, which comprises: contacting(A) at least one metal or metal compound selected from i) tungstencompounds composed of tungsten and an element of group IIIb, IVb, Vb, orVIb, ii) molybdenum compounds composed of molybdenum and an element ofgroup IIIb, IVb, Vb, or VIb, and iii) tungsten metal and molybdenummetal; (B) at least one compound selected from tertiary amine oxidecompounds and nitrogen-containing aromatic N-oxide compounds; (C)hydrogen peroxide; and (D) a phosphate compound, to obtain a metalcatalyst and then reacting a primary alcohol with hydrogen peroxide inthe presence of said metal catalyst, wherein the carbonyl compound is analdehyde and the amount of hydrogen peroxide to be used is 0.9 to 1.5moles per 1 mole of primary alcohol.
 3. A process for producing acarbonyl compound, which comprises: contacting (A) at least one metal ormetal compound selected from i) tungsten compounds composed of tungstenand an element of group IIIb, IVb, Vb, or VIb, ii) molybdenum compoundscomposed of molybdenum and an element of group IIIb, IVb, Vb, or VIb,and iii) tungsten metal and molybdenum metal; (B) at least one compoundselected from tertiary amine oxide compounds and nitrogen-containingaromatic N-oxide compounds; (C) hydrogen peroxide; and (D) a phosphatecompound, to obtain a metal catalyst and then reacting a primary alcoholwith hydrogen peroxide in the presence of said metal catalyst, whereinthe carbonyl compound is a carboxylic acid and the amount of hydrogenperoxide to be used is 1.5 moles or more per 1 mole of primary alcohol.